Anthraquinonyl-amino derivatives of benzanthronepyrazolanthrone



Patented May 10, 1932 -1:1 1). STATES PATENT,Price 5 MAX" ALBERTiKn'Nz oF MANNHEIM, AND KARL KOEBERLEgOF LUD' wIGS HAFEN-ON- GERMANY; ASSIGNORS T0 GENERAL ANILINE YORK; N; YWA CORPORATION or DELAWARE,

.ANTHRAQU-INoNYL-AMINO- DERIVATIVES or BENZANI'HRONEPYRAZOLANTERQNE. v

Namawin Application filed August a, 1930, Seria1 No. 474, 03, and in German Afi hst 14,1929".

Thepresent invention relates to vat dyestuffs derived from benzanthronepyrazolanr throne and process of'producing same.

We have found that valuable vat dyestuffs are obtained by condensing a halogen-N- benzanthronepyrazolanthrone with van organic compound corresponding to the general formula, RX1Y, wherein R is an organic radical, a -'NHgToup in which the hydrogen atom may bereplaced by an alkyl radicle, O, or and-Y hydrogen or a metal atom. Thesaidcondensing components comprise, therefore, organic compounds in which a reactive hydrogen or metal atom is attached to an organicradicleby means of nitrogen, oxygen or sulphur. VThe most important products :are the. imines, in

, particular the d'iimines in which'the same aromatic radicle, preferably such as is capable of being vatted and contains a system of at least three condensed; rings, is attached by means of -,NH-g roups twice to theN-benzanthronepyrazolanthrone radicle.

The halogen derivatives" of N-- benzanthronepyrazolanthroneemployed as initial materials may be obtained by the action of halogen or agents supplying halogen, such as for example sulphuryl' chloride, phosphorus halides, or metal halides,for example iron chloride and aluminium. chloride, in the absence of any diluent or in inorganic media, for example sulphuric acid and derivatives thereof, such as chlorosulphonic acid or o1eum,,melts of anhydrous metal halides;-in

3 particular metal chlorides,to which substances lowering the melting point may beadded. The halogenation' is preferably carried out in the presence of one-or several of the known halogenating catalysts. Particularly useful for thepu-rpose-of ourinvention are the bromo derivatives of N-benzanthronepyrazolanthrone prepared in the aforedescribed manner, particular those-bro'mo deriva- K ti-ves as dye substantially more greenishblue shades than the unsubstituted N-benzam thronepyrazolanthrone which are obtainable by bromination in acid solution, for example chlorosulphonie acid, at temperatures betweenabout'4:0 and .C'. in the presence of halogenating catalysts, for examplez'non metals, such as iodine or sulphur,"or which are produced by bromination in the absence of diluents 1 The condensation zanthronepyrazolanthrones with the before mentioned organic :compoundsfis; preferably carried out organicdiluents of high'boiI ing point, such as nitrobenzene; chloroben- "zene,'naphthalene and derivatives thereof in 60 the presence of acid-bindingagents, suchas the oxides of alkaline earth metals, or alkaline salts thereof, and ofcondensing-catalysts, for example. metals and compounds thereof, such as'copper, copper oxide,nickel, l

nickelca-rbonate" and silver oxide.) The yields are usually practically "quantitative and the reaction products are obtained almost throughout in the crystalline: form.

The imines obtained was aforedescribedv;r

may be added, aluminium" chloride the melting point of which may b'e'lowered by an addition of common salt, or caustic alkali. The-resulting dyestufi's may; be converted by the usual methods into; their 'leuco compounds as for example theirlleuco esters! The'followingexamples will further illus I trate the nature of this invention, but the invention is not restrictedx-to these examples. The parts are by weight. a a Y i Q i Example 1 I 62 parts of the dibromobenzanthronepyrazolanthrone obtainable by: treating N-benzanthronepyrazolanthrone with bromineinzch loe ;rosu1phonic acid in the presence. of iodine: at

about 40"v 0., are boiled while stirring in 1000 parts of naphthalene with 46 parts a of 1.-

parts of sodium acetate and 12 partsof 'cop per oxide, until aZ-sampletaken out is-prace tically free from bromine, .The r'eactionmixture isthen allowed-to, cool,is,diluted 1'0! bras halogen-N benaminoanthraquinone,"after the addition of 5.0 I

1 '62 parts of dibromobenzanthronepyrazolanthrone (prepared from benzanthronepyrazolanthroneby bromination in chlorosula diluent of low melting point as for example with monochlorobenzene, and the reaction product is filtered ofi' by suction. The suspending agent may also be distilled ofi, if desired under reduced pressure and/or with steam. The resulting dyestufi, which is a blue black crystalline powder, dissolves in concentrated sulphuric: acid giving a green coloration and yields powerful, gray dyeings having excellent fastness, especially to kier boiling, on cotton from a dark green vat.

By employing'the equivalent amount of 1- amino-4-benzoylaminoanthraquinone instead of I-aminoanthraquinone a product giving greenishgray dyeings is obtained. The same dyestufi' is alsoobtained by condensation of the, bromobenzanthronepyraZola-nthrone alreadydescribed in this example with 1.4:- diaminoanthraquinone and subsequent benzoylation; l

By employing Q-aminoanthraquinOne instead of 1-an 1inoanthraquinone, a dyestuff giving bluish gray dyeings is obtained.

v A similar condensation product is obtained by condensing the bromobenza-nthronepyrazolanthrone obtainable by bromination of N- ,benza-nthronepyrazolanthrone in oleum with l-aminoanthraquinone. By employing 2 molecular proportions of l -aminoanthraquinone-2-aldehyde' a dyestufi' giving greenish gray dyeings is obtained. V

Other suspending agents, such as nitroben- 1zene may be employed instead of naphthaene. r

The corresponding carbazole derivatives which have similar tinctoria-l properties but which usually have other shades of color may be obtained from these reaction products by subsequent fusion with alcoholic potash or by treatment with aluminium chloride, if desired withthe addition of common salt and while leading through a gas having an oxidizing action, such as oxygen or air.

Example 2 phonic acid at from to C. in the presence of manganeseas a catalyst) are boiled while stirring in partsv of naphthalene with 2.3 parts of l-aminoanthraquinone and 5 parts of copper acetate until all the l-aminoanthraquinone has been used up. The reaction mixture is then allowed to cool and is worked up as described in Example 1. The mono-bromo-Va-anthraquinonyl-aminobenzanthronepyrazolanthrone thus obtained is a blue black powder which dissolvesin concentrated sulphur c acid giving a green coloration and yields powerful, very fast blue gray to blue 'black dyeings from a blue-green vat. The bromine atom present in the reaction product may still be replaced by other radicles by the method according to the present invention.

. uct'is filtered off by suction; Itis bI e The condensation product from dibromobenzanthronepyrazola-nthrone (obtainableby the action of bromine on N-benzanthrone pyrazolanthrone in oleum) and 2 molecularproportions of Bz 3.5 dichloro 4 aminopared by nitrating the Bz-3.5-'dichloro .com-

pound in nitrobenzene by means of nitric acid. The Bz-3.5-dichloro compound isobtainable by treating with reducing agents the Bz 3.5 dichloroi-chloranthraquinone- 80 2.1benzacridone which may be produced by treating the unsubstituted acridone in nitrobenzene with chlorine in. the presence of iodine. Monobromobenzanthronepyrazolanthro n e (prepared by bromination of benzanthronepyrazolanthronewith 1 atomic proportion of bromine in chlorosulphonic acid with iodine as a catalyst) yields a dyestufi' giving powerful gray dyeings when condensed with l-aminoanthraquinone.

Ewample 3 30 parts of the bromobenzanthronepyrazolanthrone (obtainable as described in Exam 7 ple 1) are boiled while stirring in'lOOO parts of nitrobenzene, after the addition of 50 parts of calcined soda, 7 parts of copper oxide and 30 parts of benzamine, until the reaction product is practically free from bromine; 190 The whole is then worked up in the usual 3 manner. The resulting reaction product, whichis a dark blue green powder, dissolves in concentrated sulphuric acid giving an olive green coloration, yields a blue vat and gives ggry fast, green blue dyeings on the vegetable Substituted benzamides or the amides of the naphthalene carboxylic acids or anthraquinone carboxylic acids, or acid amides of an' even still higher molecular weight react" 1 similarly to benzamide.

With para-toluenesulphamide or potassium phthalimide, condensation'products are obtained which by treatment with acids are 11 15 5.5 parts of monobromobenzanthronepyra- Zolanthrone I (obtainable as described in the last paragraph of Example 2) are introduced at from 100 to G. into a suspension of 50 parts of phenol and 20 parts of potassium carbonate, the wholeis slowly heated to 180 C. and kept at the same temperature until the reaction is completed. The reaction mixture is then allowed to cool, the excess phenolis distilled off with steam and the reactionprod-- powder which dissolves in concentrated sulgive a green solution and dyeing cotton powphuric acid giving a blue coloration and yields fast navy blue dyeings from a blue vat.

Example 5 62 parts of the dibromo-N-benzanthronepyrazolanthrone described in Example 1 are heated to boiling while stirringin'1250 parts of nitrobenzene after the addition of parts of sodium acetate, 10 parts of copper oxide and 82 parts of the 4-amino-Bz-35-dichloroanthraquinone-2.l-benzacridone described in Example 2 until the reaction product is free from bromine. The reaction mixture is then worked up as usual. The condensation product obtained in crystalline form in a very good yield dissolves in concentrated sulphuric acid to give a brown violet solution and dyes cotton green gray very fast shades from a blue vat. V

A reactionproduct dyeing olive shades is obtained in an analogous manner from tetrabromo-N-benzanthronepyrazolanthrone.

The equivalent amount of a dichloro derivative may be employed instead of the aforesaid dibromo compound.

What we claim is:

erful, gray shades from a dark green vat.

In testimony whereof we have hereunto set our hands. v

MAX ALBERT KUNZ. KARL KOEBERLE.

1. As new articles of manufacture vat dye- V stuffs derived from N-benzanthron pyrazolanthrone corresponding to the formula:

in which R stands for an anthraquinonyl radicle, the dyestuffs dissolving in concentrated sulphuric acid to give green solutions and dyeing cotton greenish to bluish gray shades from green vats.

v2. As a new article of manufacture the vat dyestuif corresponding to the formula:

dissolving in concentrated sulphuric acid to no i 

